Research Article Enhancement of Mechanical and …downloads.hindawi.com/journals/ijms/2013/816503.pdffor Nanomer PGV shows that the presence of free water molecule vibration as H O

Hindawi Publishing CorporationIndian Journal of Materials ScienceVolume 2013 Article ID 816503 11 pageshttpdxdoiorg1011552013816503

Research ArticleEnhancement of Mechanical and ThermalProperties of Polylactic AcidPolycaprolactone Blends byHydrophilic Nanoclay

Chern Chiet Eng1 Nor Azowa Ibrahim1 Norhazlin Zainuddin1 Hidayah Ariffin2

Wan Md Zin Wan Yunus3 Yoon Yee Then1 and Cher Chean Teh1

1 Department of Chemistry Faculty of Science University Putra Malaysia 43400 UPM Serdang Selangor Malaysia2 Department of Bioprocess Technology Faculty of Biotechnology and Biomolecular Sciences University Putra Malaysia43400 UPM Serdang Selangor Malaysia

3 Chemistry Department Centre for Defence Foundation Studies National Defence University of Malaysia Kem Sungai Besi57000 Kuala Lumpur Malaysia

Correspondence should be addressed to Nor Azowa Ibrahim norazowascienceupmedumy

Received 28 August 2013 Accepted 19 November 2013

Academic Editors M Jayachandran and M Romero Perez

Copyright copy 2013 Chern Chiet Eng et al This is an open access article distributed under the Creative Commons AttributionLicense which permits unrestricted use distribution and reproduction in any medium provided the original work is properlycited

The effects of hydrophilic nanoclay Nanomer PGV on mechanical properties of Polylactic Acid (PLA)Polycaprolactone (PCL)blends were investigated and compared with hydrophobic clay Montmorillonite K10The PLAPCLclay composites were preparedby melt intercalation technique and the composites were characterized by X-ray Diffraction (XRD) Fourier Transform InfraredSpectroscopy (FTIR) Thermogravimetric Analysis (TGA) Dynamic Mechanical Analysis (DMA) Scanning Electron Microscopy(SEM) and Transmission Electron Microscopy (TEM) FTIR spectra indicated that formation of hydrogen bond betweenhydrophilic clay with the matrix XRD results show that shifting of basal spacing when clay incorporated into polymer matrixTEMmicrographs reveal the formation of agglomerate in the composites Based on mechanical properties results addition of clayNanomer PGV significantly enhances the flexibility of PLAPCL blends about 13626 TGA showed that the presence of clayimprove thermal stability of blends DMA show the addition of clay increase storage modulus and the presence of clay NanomerPGV slightly shift two 119879

119892of blends become closer suggest that the presence of clay slightly compatibilizer the PLAPCL blends

SEM micrographs revealed that presence of Nanomer PGV in blends influence the miscibility of the blends The PLAPCL blendsbecome more homogeneous and consist of single phase morphology

1 IntroductionPetroleum-based polymers such as polypropylene (PP) poly-ethylene (PE) and polystyrene (PS) cause major drawback toenvironment as these polymers tend to accumulate in dis-posal system due to these polymers are nondegradableTherefore biodegradable polymer attracted the attention ofresearcher as biodegradable polymer seems to be the bestsolution to this problem A wide range of natural or syn-thetic polymers degrade by hydrolytic (polyglycolide poly-lactides polydioxanone Polycaprolactone polyhydroxyalka-noates) or enzymatic (polysaccharides protein polyaminoacids) route [1] Although these polymers have wide range

of mechanical properties and degradation rate inappropriatestiffness or degradation rate restrict their application the-refore blending with other polymers copolymerization oradding plasticizer can be used to tune the properties of thesepolymers according to application requirements [2]

Polylactic acid (PLA) is biodegradable polymer producedfrom renewable resources as PLA is obtained from poly-merization of lactic acid monomer a fermentation productobtained from corn starch by bacterial fermentation [3] PLAhas good mechanical properties thermal plasticity and bio-compatibility However PLA is a comparatively brittle andstiff polymer with low deformation at break Therefore

2 Indian Journal of Materials Science

modification of PLA is needed in order to compete with otherflexible polymers such as polypropylene or polyethylene [4]There are many techniques to modify PLA such as copoly-merization [5 6] blending with other polymers [7 8] theaddition of plasticizers [9] the addition of nucleating agents[10] and forming composites with fiber or nanoparticles[11 12]

Polycaprolactone (PCL) is biodegradable polymer fromnonrenewable petrochemical resources which prepared byring opening polymerization of 120576-caprolactone using varietyof anionic cationic and co-ordination catalysts PCL canalso obtain from free radical ring opening polymerizationof 2-methylene-1-3-dioxepane PCL is flexible semicrystallinepolymer with low melting point and exceptional blend-compatibilityTherefore PCL can be blendedwith other poly-mers to improve stress crack resistance dye-ability and adhe-sion [13] High flexibility PCL can be considered as a goodplasticizer for PLA compared to low molecular weight plas-ticizers as it does not migrate to the surface of the blendedsamples and the physical properties cannot be debased [14]

However due to immiscibility of PLAPCL blend [15]compatibilization is needed to improve its properties Tuba etal compatibilized PLAPCL with L-lysine-diisocyanate andL-lysine-triisocyanate which enhance the fracture toughnesschanges the morphology of fracture surface become morehomogeneous and also promote crystallization and heteroge-neous nucleation of PLA [16]Hoidy et al incorporate octade-cylamine-montmorillonite (ODA-MMT) and fatty hydrox-amic acid-montmorillonite (FHA-MMT) in PLAPCL blendand the results revealed that addition of clay improve mecha-nical properties and also thermal stability of the blends [17]

The objective of this paper is to investigate the effect ofaddition two type of clay which is hydrophobicMontmorillo-nite K10 and hydrophilic Nanomer PGV on mechanical pro-perties and thermal properties of PLAPCL blend by meltintercalation Various characterization techniques such asX-ray Diffraction (XRD) Fourier Transform Infrared Spe-ctroscopy (FTIR)Thermogravimetric Analysis (TGA) Dyn-amicMechanical Analysis (DMA) Scanning ElectronMicro-scopy (SEM) and Transmission ElectronMicroscopy (TEM)used to study the effect of addition of clay on the propertiesof PLAPCL blend

2 Experimental

21 Materials All reactions were carried out by using reagentgrade chemicals (gt98 purity) without further purificationThe clay Montmorillonite K10 and Nanoclay hydrophilicbentonite (Nanomer PGV) was purchased from Sigma-Ald-rich and used as received Polylactide Resin 4060D was sup-plied by NatureWorks while Polycaprolactone (CAPA 650)was supplied by Solvay Caprolactone

22 Preparation of PLAPCLClay Nanocomposites The nan-ocomposite was prepared by melt blending technique Thecomposition of PLA and PCL kept constant at 85wtand 15wt respectively while the clay content was variedbetween 0 to 7wt PLA PCL and clay were manually pre-mixed in a container and fed into Brabender Plastograph

EC at 170∘C with rotor speed of 50 rpm for 10 minutesThe products were then compression moulded into sheets of1mm (for tensile properties) or 3mm (for flexural propertiesand izod impact resistance) thickness by an electricallyheated hydraulic press with a force of 1500 kN at 160∘C for10 minutes The sample sheets were then used for furthercharacterization

23 Fourier Transform Infrared Spectroscopy (FTIR) PerkinElmer Spectrum 100 series spectrometer equipped withattenuated total reflectance (ATR) was used to determine thefunctional groups and types of the bonding of the samplesThe infrared spectra were recorded in the range of frequencyof 280 to 4000 cmminus1

24 X-Ray Diffraction (XRD) X-Ray Diffraction measure-ment to determine the 119889-spacing of the clay was carried outby using XrsquoPERT PRO PW3040 where Cu K120572 (120582 = 15406 A)beam operated at 40mA and 45 kV with the data recorded in2120579 range of 2∘ to 10∘ using the scan rate of 2∘min

25 Transmission ElectronMicroscope (TEM) TheTransmis-sion Electron Micrographs of the thin layer of the nanocom-posites were recorded by Hitachi H-7100 TEM which oper-ated at an accelerating voltage of 100 kVThe thin layer of sam-ples was prepared by using a Reichert Jung Ultracut E mic-rotome equipped with cryosectioning unit whereas the sam-ples were sliced into thin layer of about 90 nm by a diamondknife cooled at minus120∘C with liquefied nitrogen

26 Tensile Properties Tensile properties were measuredwith Instronmachinemodel 4301 with grip attachment dista-nce of 45mm Load of 10 kN was applied at constant cros-shead speed of 5mmminminus1 Data was processed with com-puterized Instron (Software series 9 national instrumentsGPIB PC22a and NI-4882) Test specimen were preparedand stamped in accordance to ASTMD638 dumbbell param-eters Sample thickness was measure with Mitutoyo Digi-matic Indicator type IDF-112 having measuring accuracy ofplusmn0001mm

27 Flexural Properties The flexural strength and flexuralmodulus were measured with Instron Universal TestingMachine 4301 according to ASTMD790The size of the sam-ples testing is 127mm times 127mm times 3mm The crossheadspeed is 13mmmin and the support span length is 48mmData was processed with computerized Instron (Softwareseries 9 national instruments GPIB PC22a and NI-4882)

28 Izod Impact Resistance The Izod impact test was carriedout according to ASTMD256 standard using an impact tester(IZOD Impact Tester) The sample size is 635 times 127 times 3mmwhile the notch length is 254mm The energy required tobreak the samples was divided by unit area of residual cross-section of sample to obtain impact resistance value Theimpact strength (Jm) was calculated by dividing the energyobtained (J) with the thickness of specimen (m)

Indian Journal of Materials Science 3Re

lativ

e int

ensit

y

3000 10002000

361128 cmminus1

340254 cmminus1

337560 cmminus1

163583 cmminus1

163308 cmminus1

79549 cmminus1

Wavenumber (cmminus1)

MMT K10

Nanomer PGV

Figure 1 FTIR spectra of Montmorillonite K10 and Nanomer PGV

29Thermogravimetric Analysis (TGA) Perkin Elmer TGA7was used for Thermogravimetic Analysis of samples wherethe mass of samples about 15mg and were heated from 35∘Cto 800∘C with the heating rate of 10∘Cmin Nitrogen gas waspumped with the flow rate of 20mLmin in order to let theanalysis carry out in nitrogen atmosphere

210 Dynamic Mechanical Analysis (DMA) Dynamic Mec-hanical Analyzer Perkin Elmer Model Pyris Diamond DMAwas used Samples were tested under the condition of staticforce 10N dynamic force 8N with 1Hz frequencies Scanwas done from minus100∘C to 130∘C at 2∘Cmin rate with sampledimensions were 1mm thickness and 30mm length by usingbending mode

211 Scanning Electron Microscopy (SEM) The surface mor-phology of fracture surfaces of tensile test specimenwas obse-rved with Scanning Electron Microscope JEOL JSM-6400with the samples were sputter coated with gold using Bio-radcoating system before viewing

3 Results and Discussion

31 Characterization of Clay

311 Fourier Transform Infrared Spectroscopy (FTIR) FTIRspectra of Montmorillonite K10 and Nanomer PGV areshown in Figure 1Thepresence of broad band at 361128 cmminus1for Nanomer PGV shows that the presence of free watermolecule vibration as HndashOndashH stretching of water moleculespresent in the interlayer region of clay which indicatesthat Nanomer PGV is hydrophilic However FTIR spec-tra indicates that Montmorillonite K10 is hydrophobic asthe intensity of free OndashH stretching peak is low Band at163308 cmminus1 and 163583 cmminus1 for Montmorillonite K10 andNanomer PGV correspond to OH deformation of water[18] Besides a unique characteristic peak at 79549 cmminus1for Montmorillonite K10 correspond to quartz symmetricalstretching as mention by Ravisankar et al [19] indicates thepresence of quartz in the clay Montmorillonite K10 andNanomer PGV exhibits similar peak correspond to OndashHstretching (337560 cmminus1 and 340254 cmminus1) SindashO stretching(103223 and 98278 cmminus1) and SindashO bending (44728 and40615 cmminus1) respectively

4 6 8 10

10000

2500

0

Cou

nts

Montmorillonite K10Nanomer PGV

Position 2120579 (∘)

Figure 2 XRDpatterns ofMontmorillonite K10 andNanomer PGV

0

20

40

60

80

100

120

0 200 400 600 800 1000 1200

Wei

ght (

)

MMT K10PGV

Temperature (∘C)

Figure 3 TG thermogram of Montmorillonite K10 and NanomerPGV

Table 1 Basal spacing of Montmorillonite K10 and Nanomer PGV

Clay 2120579 (∘) Basal spacing (nm)Montmorillonite K10 8967 0985Nanomer PGV 6043 1461

312 X-RayDiffraction (XRD) TheXRDpatterns of clays areillustrated in Figure 2 Montmorillonite K10 has 0985 nm ofbasal spacing at 2120579 = 8967∘ while Nanomer PGV has highervalue of basal spacing which is 1461 nm at 2120579 = 6043∘ Thevalue of 2120579 and basal spacing of clays are summarized inTable 1

313 Thermogravimetric Analysis (TGA) The TG and DTGthermogramof clayMontmorillonite K10 andNanomer PGVare shown in Figures 3 and 4 respectively Decompositionof both clays shows two thermal decomposition steps Thefirst step is desorption of water from interlayer space whicharound 200∘C Clay Nanomer PGV shows the percentage of


MMT K10PGV

0 200 400 600 800 1000 1200

minus350E minus 04

minus300E minus 04

minus250E minus 04

minus200E minus 04

minus150E minus 04

minus100E minus 04

minus500E minus 05

000E + 00

Figure 4 DTG thermogram of Montmorillonite K10 and NanomerPGV

Rela

tive i

nten

sity

PLAPCL

PLAPCLMMT K10

PLAPCLPGV

3000 10002000

174829 cmminus1

174835 cmminus1

174791 cmminus1

327983 cmminus1


Figure 5 FTIR spectra of PLAPCL1 wt clay composites

weight loss (118) higher than Montmorillonite K10 (3)during the first degradation steps which proved that ClayNanomer PGV is more hydrophilic than MontmorilloniteK10 The second step is dehydroxylation of the layer crystallattice structure which around 700∘C [20] The percentage ofweight loss for Montmorillonite K10 and Nanomer PGV atthis stage is 29 and 39 respectively

32 Characterization of PLAPCLClay Composites

321 Fourier Transform Infrared Spectroscopy (FTIR)Figure 5 shows the infrared spectra of PLAPCL andPLAPCL1 wt clay composites The spectra shows thatall three composites exhibited strong absorbance peak aro-und 1748 cmminus1 which correspond to the vibration of carb-onyl group C=O stretching Peak at 327983 cmminus1 indi-cated hydrogen bonded OndashH stretching present at PLAPCLNanomer PGV composites which suggest that somehydrogen bond formed between hydrophilic clay with the

Rela

tive i

nten

sity

5 102120579 (∘)

MMT K10-PLA-PCL (7)

MMT K10-PLA-PCL (5)

MMT K10-PLA-PCL (3)

MMT K10-PLA-PCL (1)

MMT K10

Figure 6 XRD patterns of Montmorillonite K10 and PLAPCLcomposites at different clay loadings

Rela

tive i

nten

sity

5 102120579 (∘)

NPGV-PLA-PCL (7)

NPGV-PLA-PCL (5)

NPGV-PLA-PCL (3)

NPGV-PLA-PCL (1)

NPGV

Figure 7 XRDpatterns ofNanomer PGVandPLAPCL compositesat different clay loadings

matrix This might due to PLA consists of OH bond at theend of the polymer chain which can form hydrogen groupwith the hydrophilic clay

322 X-Ray Diffraction (XRD) Figure 6 shows the XRDpattern of Montmorillonite K10 and PLAPCLMontmo-rillonite K10 composites at different clay loading For Mont-morillonite K10 the basal spacing of composites with clayloading of 1 wt to 5wt could not be detected whichmight due to low clay content in composites or absenceof any ordered layer structure as the result of exfoliationand random distribution of the clay platelets within polymerblend Generally exfoliated system is more feasible withlower clay content while intercalated system more frequentlyobserved for nanocomposites with higher clay content [21]The diffraction angle of Montmorillonite K10 is shiftedfrom 8967∘ (0985 nm) to 8855∘ (0998 nm) for 7wt ofMontmorillonite K10 in PLAPCL blends

The XRD pattern of Nanomer PGV and PLAPCLNanomer PGV composites at different clay loading illustratedin Figure 7 The basal spacing of Nanomer PGV increasefrom 1461 nm (6043∘) to 1532 nm (5765∘) 1564 nm (5645∘)and 1584 nm (5575∘) when 3wt 5wt and 7wt of clayadded into polymer blends respectively All basal spacing

Indian Journal of Materials Science 5

100 nm

(a)

100 nm

(b)

Figure 8 TEMmicrographs of (a) PLAPCL1 wt Montmorillonite K10 and (b) PLAPCL1 wt Nanomer PGV

Table 2 Basal spacing of PLAPCL composites at various clayloadings

Sample 2120579 (∘) Basal spacing (nm)Clay MMT K10 8967 0985PLAPCL1 wt MMT K10 mdash mdashPLAPCL3wt MMT K10 mdash mdashPLAPCL5wt MMT K10 mdash mdashPLAPCL7wt MMT K10 8855 0998Clay NPGV 6043 1461PLAPCL1 wt NPGV mdash mdashPLAPCL3wt NPGV 5765 1532PLAPCL5wt NPGV 5645 1564PLAPCL7wt NPGV 5575 1584

of Montmorillonite K10 and Nanomer PGV composites aresummarized at Table 2 The increase of the basal spacingof the composites compared to the corresponding neat clayindicated that the PLAPCL chains were intercalated into theclaymatrix duringmelt intercalationThepeak of clay presentin the composites confirms the formation of composites

323 Transmission Electron Microscope (TEM) The Trans-mission Electron Micrograph of (a) PLAPCL1 wt Mont-morillonite K10 and (b) PLAPCL1 wt Nanomer PGV isshown in Figure 8 The dark area represents the intercalatedclay layers Montmorillonite K10 (Figure 8(a)) agglomeratestend to form throughout polymer matrix which inhibitsgood surface contact between polymer and clay as theincomplete dispersal of reinforcing phase in composites[22] Therefore phase separated microcomposites is formedThis observation support the XRD result which shows lit-tle shifting of diffraction peak of Montmorillonite K10 inPLAPCLMontmorillonite K10 composites Nanomer PGV(Figure 8(b)) also form agglomerates in PLAPCL matrixThe result of XRD show increment of basal spacing when clayis added into matrix which suggest that the possibility of theformation of intercalated type nanocomposites but there is

0

10

20

30

40

50

60

0 2 4 6 8

Tens

ile st

reng

th (M

Pa)

Clay loading ()

MMT K10PGV

Figure 9 Tensile strength of PLAPCLclay nanocomposites

no direct evidence proof that the formation nanocompositesfrom TEMmicrographs

324 Tensile Properties The tensile strength of PLAPCLclay composites is shown in Figure 9 When 1 of clay Mont-morillonite K10 and Nanomer PGV added into the blendsthe tensile strength increase about 1382 (5229MPa) and1689 (5514MPa) respectively compared to the unfilledPLAPCL blends (4574MPa) On the other hand whenhigher amount of clay added into the blends the tensile stre-ngth decrease gradually When small amount of clay addedinto polymer matrix the clay is located in the interphasebetween the matrix and the dispersed phase Besides incor-poration of clay increase interfacial adhesion thus compatibi-lization at a molecular level is achieved which improves stresstransfer within composites and then cause tensile strengthincrease [23] However further increase the clay content


MMT K10PGV

0

200

400

600

800

1000

1200

0 2 4 6 8

Tens

ile m

odul

us (M

Pa)

Clay loading ()

Figure 10 Tensile modulus of PLAPCLclay nanocomposites

decrease the tensile strength as part of the clay located inthe interfacial area while the excess clay is dispersed in thematrix which cause decrease in homogeneity and formationof agglomeration which decrease the tensile strength [24]

Figure 10 shows the effect of clay loading on the ten-sile modulus of PLAPCL blends The tensile modulus ofPLAPCL blends increases from 90857MPa to 104967MPawhen 1wt Montmorillonite K10 is added while the addi-tion of 1 wt Nanomer PGV increases tensile modules ofblends from 90857MPa to 95685MPa The tensile modulusdecreases when higher amount of clay is added Montmo-rillonite silicate has been found to be efficient in stiffeningpolymers [25] As high-aspect ratio of clay (1 wt) thesurface area exposed to the polymer is huge and the regionof the polymer matrix is physisorbed on the silicate surfacethus stiffened through its affinity for and adhesion on the fillersurfaces [26]

The relation between elongation at break and clay loadingis illustrated in Figure 11 The addition of 1 Nanomer PGVsignificantly increases the elongation at break of PLAPCLblends from 182mm to 430mm with the increment around13626 However the elongation at break of PLAPCLblends decrease when Montmorillonite K10 is added Whenhigher amount of clay added into the blends the elongationat break decreases for both clay This might due to existenceof large agglomerates which makes composites become morebrittle From the results obtained it can be concluded thathydrophilicNanomer PGV makes PLAPCL blends moreflexible whichmight due to hydrophilic claymore compatibleto blends

325 Flexural Properties Flexural Strength of PLAPCLclaycomposites are shown in Figure 12 Addition of 1 Mont-morillonite K10 and 1 Nanomer PGV increase the flex-ural strength of blends from 42523MPa to 48645MPa

0

1

2

3

4

5

6

0 2 4 6 8

Elon

gatio

n at

bre

ak (m

m)

Clay loading ()

MMT K10PGV

Figure 11 Elongation at break of PLAPCLclay nanocomposites

0

10

20

30

40

50

60

0 2 4 6 8

Flex

ural

stre

ngth

(MPa

)

Clay loading ()

MMT K10PGV

Figure 12 Flexural strength of PLAPCLclay nanocomposites

and 50930MPa respectively When higher amount of clayincorporated into the blend flexural strength decreases Theoverall flexural strength of Nanomer PGV composites ishigher than Montmorillonite K10 This might due to betterinterfacial adhesion between matrix and filler which willimprove stress transfer from matrix to filler resulting highervalues of flexural strength Existence of agglomerates whenhigher amount of clay is added reduces flexural strength ofcomposites

Figure 13 illustrated the flexural modulus of the com-posites where Montmorillonite K10 composites shows highervalue of flexural modulus than Nanomer PGV composites


0

500

1000

1500

2000

2500

3000

3500

0 2 4 6 8

Flex

ural

mod

ulus

(MPa

)

Clay loading ()

MMT K10PGV

Figure 13 Flexural modulus of PLAPCLclay nanocomposites

0 2 4 6 8Clay loading ()

MMT K10PGV

0

50

100

150

200

250

300

350

400

450

Impa

ct st

reng

th (J

m)

Figure 14 Impact strength of PLAPCLclay nanocomposites

Montmorillonite K10 improves flexural modulus of blendsfrom 243766MPa to 282450MPa while Nanomer PGVimproves flexural modulus to 246300MPa The inherentstiffness of Montmorillonite K10 may positively contributeto the overall stiffness of the composites which increase theflexural modulus of composites

326 Izod Impact Resistance The relation between impactstrength and clay loading is illustrated in Figure 14 When 1of Nanomer PGVwas added into matrix the impact strengthincrease from 18870 Jm to 35778 Jm with the incrementabout 8961 The addition of 1 Montmorillonite K10 also

0

20

40

60

80

100

120

0 200 400 600 800

Wei

ght (

)

PLAPCLMMT K10PGV

Temperature (∘C)

Figure 15 TG thermogram of PLAPCL blends and its clay nano-composites

increase the impact strength of matrix from 18870 Jm to24275 Jm (2864) When excess of Nanomer PGV andMontmorillonite K10 added into matrix the impact strengthof matrix decrease respectively The overall impact strengthof Nanomer PGV composites are higher than Montmoril-lonite K10 composites Better interfacial adhesion betweenclay with matrix at high-aspect ratio of clay (1 wt) resultingbetter stress transfer between matrix and clay which improveimpact strength of the matrix

327 Thermogravimetric Analysis (TGA) Figures 15 and16 illustrated the TG and DTG thermogram of PLAPCLblends and PLAPCLclay composites The PLAPCL blendshows onset temperature of 248∘C is increase to 259∘C and258∘C with maximum degradation temperature at 417∘Cand 415∘C when clay Montmorillonite K10 and NanomerPGV incorporated into the blend respectively Thereforethe incorporation of clay into polymer matrix successfullyimproves thermal stability of PLAPCL blends

The improvement in thermal stability due to clay canhinder the permeability of volatile degradation products outof the materials The dispersed clay generates a barrier whichdelays the release of thermal degradation products in com-parison the neat polymer [27] Various theories models beenproposed to explain the improvement in barrier properties ofpolymerclay composites Nielsen develop a theory to explainthe improved barrier properties of polymer-clay compositeswhich focuses on a tortuous path around the clay platesforcing the gas permeant to travel a longer path to diffusethrough the film According to the theory the increase inpath length is a function of the high-aspect ratio of the clayfiller and the volume percentage of the filler in the composite[28] However many deviations on Nielsenrsquos theory can be


PLAPCLMMT K10PGV

0 200 400 600 800

minus350E minus 03

minus300E minus 03

minus250E minus 03

minus200E minus 03

minus150E minus 03

minus100E minus 03

minus500E minus 04

000E + 00

500E minus 04

Figure 16 DTG thermogram of PLAPCL blends and its claynanocomposites

0

10000

20000

30000

40000

50000

60000

70000

80000

90000

minus150 minus100 minus50 0 50 100 150

PLAPCLMMT K10PGV

Temperature (∘C)

Stor

age m

odul

usG

998400(P

a)

Figure 17 Storage modulus of PLAPCL blends and its clay nano-composites

explained by factors such as less than complete exfoliation orpoor orientations [29] Beall proposed a new model whichprovides a correction factor applicable to Nielsenrsquos model Inthis model polymer clay interface acts as a governing factorin addition to the tortuous path [30]

328 Dynamic Mechanical Analysis (DMA) The storagemodulus (1198661015840) of PLAPCL and PLAPCLclay composite areshown in Figure 17 The incorporation of all clay increasethe 1198661015840 of PLAPCL blends where clay Montmorillonite K10shows highest increment of 1198661015840 The 1198661015840 results shows agree-ment with the tensile modulus results as Montmorillonite

0

2000

4000

6000

8000

10000

12000


PLAPCLMMT K10PGV

Temperature (∘C)

Stor

age m

odul

usG

998400998400(P

a)

Figure 18 Loss modulus of PLAPCL blends and its clay nanocom-posites

0

05

1

15

2

25

3

35

tan120575


PLAPCLMMT K10PGV

Temperature (∘C)

Figure 19 tan 120575 of PLAPCL blends and its clay nanocomposites

K10 composites shows highest tensile modulus The additionof clay show considerable effect on the elastic propertiesof polymer matrix The increment of 1198661015840 indicate that theincorporation of clay induces reinforcement effects of thematrix due to high dispersion and compatibility of matrixwith fillers [31]

Figure 18 shows loss modulus (11986610158401015840) of PLAPCL andPLAPCLclay composite The peak intensity of 11986610158401015840 repre-sents the melt viscosity of the polymer The incorporationof both clays enhances melt viscosity of the composites Thisis due to well-separated high-aspect ratio of silicate plateletsincrease the viscosity of the melt [32] The increment of melt


(a) (b) (c)

Figure 20 SEM micrograph of (a) PLAPCL (b) PLAPCL1 wt Montmorillonite K10 and (c) PLAPCL1 wt Nanomer PGV

viscosity been assigned to the expansion and delaminationof clay layers and structure formation between the layers dueto strong hydrogen bond interaction at the edge to edge andedge to face contacts which restrict themovement of polymerchain [33] Both of the clay composites exhibits two peakindicate 119879119892 of PLA and PCL in composites which proof thatthe composites is immiscible The presence of clay NanomerPGV slightly shift 119879119892 of blends from minus688

∘C to minus649∘C atPCL region and also from 478∘C to 475∘C at PLA regionsuggest that the presence of clay slightly compatibilizer thePLAPCL blends The incorporation of clay MontmorilloniteK10 also shifts 119879119892 of blends at PCL region to minus670∘C butshows no shifting of 119879119892 at PLA region

The loss factor (tan 120575) of PLAPCL and PLAPCLclaycomposite are illustrated in Figure 19The sharp peak around48∘C for the PLAPCL blends and PLAPCLclay compositescorresponds to rapid storage energy loss A small peak ataround 90∘C might due to density modulation preceding theformation of a precrystallization phase of PLA in composites[34] The area underneath tan 120575 peak indicates the dampingability of materials The area underneath tan 120575 peak showsthat PLAPCL blends and PLAPCLclay composites havealso similar area which indicated that they possessed almostsimilar damping abilities

329 Scanning ElectronMicroscopy (SEM) SEMmicrographof fractured surface of (a) PLAPCL (b) PLAPCL1 wtMontmorillonite K10 and (c) PLAPCL1 wt NanomerPGV are show in Figure 20 at magnification of 500XFigure 20(a) shows that PLAPCL blends formed continuousphase stretchable before it breaks with some small void onsurface as PLAPCL are immiscible polymer blends When1wt Montmorillonite K10 added to the blends matrix isnot well stretched before it breaks and continuous phaseformed with some void present on the surface (Figure 20(b))which indicated incompatibility ofMontmorillonite K10 withthe matrix As shown in Figure 20(c) PLAPCLNanomerPGV composites showed more homogeneous well stretchedbefore breaks and single phase morphology which indicatesgood interaction of components in the matrix

4 Conclusion

The incorporation of hydrophilic clay Nanomer PGV suc-cessfully enhance mechanical properties of PLAPCL blends

and makes it become more flexible while the addition of clayMontmorillonite K10 makes PLAPCL blends become stifferFTIR results revealed formation of hydrogen bond betweenhydrophilic clay with the matrix XRD results show that theaddition of Nanomer PGV increase of the basal spacing ofthe composites compared to the corresponding neat claywhich implies that the PLAPCL chainsmight be intercalatedinto the clay matrix after mixing but there is no clearevidence fromTEMmicrographs to support the formation ofintercalated types of nanocomposites For MontmorilloniteK10 XRD result shows little shifting of diffraction peak ofMontmorillonite K10 in composites while TEM results showsthat the formation agglomerates throughout polymer matrixindicate phase separatedmicrocomposites formwhenMont-morillonite K10 was added to the blend SEM micrographsrevealed that incompatibility of Montmorillonite K10 withthe matrix while the addition of Nanomer PGV in blendsinfluence the morphology become more homogeneous andsingle phase morphology TGA showed that the presenceof both type of clay improve thermal stability of blendsDMA show the addition of clay increase storagemodulus andthe presence of clay Nanomer PGV slightly shift two 119879119892 ofblends become closer suggest that the presence of clay slightlycompatibilizer the PLAPCL blends

Conflict of Interests

The authors declare that there is no conflict of interest withany financial organization regarding the materials discussedin the paper

Acknowledgments

The authors would like to thank the Research UniversityGrant Scheme (RUGS) UPM for their financial support Alltechnical staffs in the Department of Chemistry Faculty ofScience University PutraMalaysia are greatly acknowledgedfor their kind assistance

References

[1] L S Nair and C T Laurencin ldquoBiodegradable polymers as bio-materialsrdquo Progress in Polymer Science vol 32 no 8-9 pp 762ndash798 2007


[2] A C Vieira A TMarques RM Guedes andV Tita ldquoMaterialmodel proposal for biodegradable materialsrdquo Procedia Engi-neering vol 10 pp 1597ndash1602 2011

[3] B Gupta N Revagade and J Hilborn ldquoPoly(lactic acid) fiberan overviewrdquo Progress in Polymer Science vol 32 no 4 pp 455ndash482 2007

[4] H Balakrishnan A Hassan M U Wahit A A Yussuf and SB A Razak ldquoNovel toughened polylactic acid nanocompositemechanical thermal and morphological propertiesrdquo Materialsand Design vol 31 no 7 pp 3289ndash3298 2010

[5] H Fukuzaki M Yoshida M Asano et al ldquoSynthesis of low-molecular-weight copoly(l-lactic acid120576-caprolactone) by directcopolycondensation in the absence of catalysts and enzymaticdegradation of the polymersrdquo Polymer vol 31 no 10 pp 2006ndash2014 1990

[6] D W Grijpma and A J Pennings ldquo(Co)polymers of L-lactide1 Synthesis thermal properties and hydrolytic degradationrdquoMacromolecular Chemistry and Physics vol 195 no 5 pp 1633ndash1647 1994

[7] H ChenM Pyda and P Cebe ldquoNon-isothermal crystallizationof PETPLA blendsrdquoThermochimica Acta vol 492 no 1-2 pp61ndash66 2009

[8] T Yokohara and M Yamaguchi ldquoStructure and properties forbiomass-based polyester blends of PLA and PBSrdquo EuropeanPolymer Journal vol 44 no 3 pp 677ndash685 2008

[9] V S G Silverajah N A Ibrahim W W M Z Yunus HA Hassan and C B Woei ldquoA comparative study on themechanical thermal and morphological characterization ofpoly(lactic acid)epoxidized palm oil blendrdquo International Jour-nal of Molecular Sciences vol 13 no 5 pp 5878ndash5898 2012

[10] Y Phuphuak and S Chirachanchai ldquoSimple preparation ofmulti-branched poly(l-lactic acid) and its role as nucleatingagent for poly(lactic acid)rdquo Polymer vol 54 no 2 pp 572ndash5822013

[11] S Ochi ldquoMechanical properties of kenaf fibers and kenafPLAcompositesrdquo Mechanics of Materials vol 40 no 4-5 pp 446ndash452 2008

[12] J-W Rhim S-I Hong and C-S Ha ldquoTensile water vapor bar-rier and antimicrobial properties of PLAnanoclay compositefilmsrdquo LWTmdashFood Science and Technology vol 42 no 2 pp612ndash617 2009

[13] M A Woodruff and D W Hutmacher ldquoThe return of a forgot-ten polymermdashpolycaprolactone in the 21st centuryrdquo Progress inPolymer Science vol 35 no 10 pp 1217ndash1256 2010

[14] J-T Yeh C-J Wu C-H Tsou et al ldquoStudy on the crys-tallization miscibility morphology properties of poly(lacticacid)poly(120576-caprolactone) blendsrdquo Polymer vol 48 no 6 pp571ndash578 2009

[15] D Wu Y Zhang M Zhang andW Zhou ldquoPhase behavior andits viscoelastic response of polylactidepoly(120576-caprolactone)blendrdquo European Polymer Journal vol 44 no 7 pp 2171ndash21832008

[16] F Tuba L Olah and P Nagy ldquoCharacterization of reactivelycompatibilized poly(dl-lactide)poly(120576-caprolactone) biode-gradable blends by essential work of fracturemethodrdquoEngineer-ing Fracture Mechanics vol 78 no 17 pp 3123ndash3133 2011

[17] W H Hoidy M B Ahmad E A J Al-Mulla and N AB Ibrahim ldquoPreparation and characterization of polylactic

acidpolycaprolactone clay nanocompositesrdquo Journal of AppliedSciences vol 10 no 2 pp 97ndash106 2010

[18] J Madejova and P Komadel ldquoBaseline studies of the clayminerals society source clays infraredmethodsrdquoClays andClayMinerals vol 49 no 5 pp 410ndash432 2001

[19] R Ravisankar S Kiruba P Eswaran G Senthilkumar andA Chandrasekaran ldquoMineralogical characterization studies ofancient potteries of Tamilnadu India by FT-IR spectroscopictechniquerdquo E-Journal of Chemistry vol 7 no 1 pp S185ndashS1902010

[20] R R Tiwari K C Khilar and U Natarajan ldquoSynthesis andcharacterization of novel organo-montmorillonitesrdquo AppliedClay Science vol 38 no 3-4 pp 203ndash208 2008

[21] AKNikolaidis D S Achilias andG PKarayannidis ldquoEffect ofthe type of organic modifier on the polymerization kinetics andthe properties of poly(methyl methacrylate)organomodifiedmontmorillonite nanocompositesrdquo European Polymer Journalvol 48 no 2 pp 240ndash251 2012

[22] N A Ibrahim B W Chieng and W M Z Wan YunusldquoMorphology thermal and mechanical properties of biodegra-dable poly(butylene succinate)poly(butylene adipate-co-tere-phthalate)clay nanocompositesrdquo Polymer vol 49 no 15 pp1571ndash1580 2010

[23] H Essawy and D El-Nashar ldquoThe use of montmorillonite asa reinforcing and compatibilizing filler for NBRSBR rubberblendrdquo Polymer Testing vol 23 no 7 pp 803ndash807 2004

[24] S N Sathe G S Srinivasa Rao K V Rao and S Devi ldquoTheeffect of composition onmorphological thermal andmechani-cal properties of polypropylenenylon-6polypropylene-g-butylacrylate blendsrdquoPolymer Engineering and Science vol 36 no 19pp 2443ndash2450 1996

[25] J Wang and R Pyrz ldquoPrediction of the overall moduli of lay-ered silicate-reinforced nanocomposites-part I basic theoryand formulasrdquo Composites Science and Technology vol 64 no7-8 pp 925ndash934 2004

[26] Z Yu J Yin S Yan Y Xie J Ma and X Chen ldquoBiodegrad-able poly(l-lactide)poly(120576-caprolactone)-modifiedmontmoril-lonite nanocomposites preparation and characterizationrdquo Poly-mer vol 48 no 21 pp 6439ndash6447 2007

[27] T Agag T Koga and T Takeichi ldquoStudies on thermaland mechanical properties of polyimide-clay nanocompositesrdquoPolymer vol 42 no 8 pp 3399ndash3408 2001

[28] C Silvestre D Duraccio and S Cimmino ldquoFood packagingbased on polymer nanomaterialsrdquo Progress in Polymer Sciencevol 36 no 12 pp 1766ndash1782 2011

[29] K Majeed M Jawaid A Hassan et al ldquoPotential materialsfor food packaging from nanoclaynatural fibres filled hybridcompositesrdquoMaterials amp Design vol 46 pp 391ndash410 2013

[30] D Adame and G W Beall ldquoDirect measurement of the cons-trained polymer region in polyamideclay nanocomposites andthe implications for gas diffusionrdquo Applied Clay Science vol 42no 3-4 pp 545ndash552 2009

[31] K Fukushima D Tabuani and G Camino ldquoNanocompositesof PLA and PCL based on montmorillonite and sepioliterdquoMaterials Science andEngineeringC vol 29 no 4 pp 1433ndash14412009

[32] S Boucard J Duchet J F Gerard P Prele and S GonzalezldquoProcessing of polypropylene-clay hybridsrdquo MacromolecularSymposia vol 194 no 1 pp 241ndash246 2003


[33] X Fu and S Qutubuddin ldquoPolymer-clay nanocomposites exfo-liation of organophilic montmorillonite nanolayers in poly-styrenerdquo Polymer vol 42 no 2 pp 807ndash813 2001

[34] F Cock A A Cuadri M Garcıa-Morales and R Partai ldquoThe-rmal rheological and microstructural characterisation of com-mercial biodegradable polyestersrdquo Polymer Testing vol 32 no4 pp 716ndash723 2013

Submit your manuscripts athttpwwwhindawicom

ScientificaHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

CorrosionInternational Journal of

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Polymer ScienceInternational Journal of



CeramicsJournal of


CompositesJournal of

NanoparticlesJournal of



International Journal of

Biomaterials


NanoscienceJournal of

TextilesHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Journal of

NanotechnologyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Journal of

CrystallographyJournal of


The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014


CoatingsJournal of

Advances in

Materials Science and EngineeringHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Smart Materials Research



MetallurgyJournal of


BioMed Research International

MaterialsJournal of


Nano

materials


Journal ofNanomaterials


modification of PLA is needed in order to compete with otherflexible polymers such as polypropylene or polyethylene [4]There are many techniques to modify PLA such as copoly-merization [5 6] blending with other polymers [7 8] theaddition of plasticizers [9] the addition of nucleating agents[10] and forming composites with fiber or nanoparticles[11 12]

Polycaprolactone (PCL) is biodegradable polymer fromnonrenewable petrochemical resources which prepared byring opening polymerization of 120576-caprolactone using varietyof anionic cationic and co-ordination catalysts PCL canalso obtain from free radical ring opening polymerizationof 2-methylene-1-3-dioxepane PCL is flexible semicrystallinepolymer with low melting point and exceptional blend-compatibilityTherefore PCL can be blendedwith other poly-mers to improve stress crack resistance dye-ability and adhe-sion [13] High flexibility PCL can be considered as a goodplasticizer for PLA compared to low molecular weight plas-ticizers as it does not migrate to the surface of the blendedsamples and the physical properties cannot be debased [14]

However due to immiscibility of PLAPCL blend [15]compatibilization is needed to improve its properties Tuba etal compatibilized PLAPCL with L-lysine-diisocyanate andL-lysine-triisocyanate which enhance the fracture toughnesschanges the morphology of fracture surface become morehomogeneous and also promote crystallization and heteroge-neous nucleation of PLA [16]Hoidy et al incorporate octade-cylamine-montmorillonite (ODA-MMT) and fatty hydrox-amic acid-montmorillonite (FHA-MMT) in PLAPCL blendand the results revealed that addition of clay improve mecha-nical properties and also thermal stability of the blends [17]

The objective of this paper is to investigate the effect ofaddition two type of clay which is hydrophobicMontmorillo-nite K10 and hydrophilic Nanomer PGV on mechanical pro-perties and thermal properties of PLAPCL blend by meltintercalation Various characterization techniques such asX-ray Diffraction (XRD) Fourier Transform Infrared Spe-ctroscopy (FTIR)Thermogravimetric Analysis (TGA) Dyn-amicMechanical Analysis (DMA) Scanning ElectronMicro-scopy (SEM) and Transmission ElectronMicroscopy (TEM)used to study the effect of addition of clay on the propertiesof PLAPCL blend

2 Experimental

21 Materials All reactions were carried out by using reagentgrade chemicals (gt98 purity) without further purificationThe clay Montmorillonite K10 and Nanoclay hydrophilicbentonite (Nanomer PGV) was purchased from Sigma-Ald-rich and used as received Polylactide Resin 4060D was sup-plied by NatureWorks while Polycaprolactone (CAPA 650)was supplied by Solvay Caprolactone

22 Preparation of PLAPCLClay Nanocomposites The nan-ocomposite was prepared by melt blending technique Thecomposition of PLA and PCL kept constant at 85wtand 15wt respectively while the clay content was variedbetween 0 to 7wt PLA PCL and clay were manually pre-mixed in a container and fed into Brabender Plastograph

EC at 170∘C with rotor speed of 50 rpm for 10 minutesThe products were then compression moulded into sheets of1mm (for tensile properties) or 3mm (for flexural propertiesand izod impact resistance) thickness by an electricallyheated hydraulic press with a force of 1500 kN at 160∘C for10 minutes The sample sheets were then used for furthercharacterization

23 Fourier Transform Infrared Spectroscopy (FTIR) PerkinElmer Spectrum 100 series spectrometer equipped withattenuated total reflectance (ATR) was used to determine thefunctional groups and types of the bonding of the samplesThe infrared spectra were recorded in the range of frequencyof 280 to 4000 cmminus1

24 X-Ray Diffraction (XRD) X-Ray Diffraction measure-ment to determine the 119889-spacing of the clay was carried outby using XrsquoPERT PRO PW3040 where Cu K120572 (120582 = 15406 A)beam operated at 40mA and 45 kV with the data recorded in2120579 range of 2∘ to 10∘ using the scan rate of 2∘min

25 Transmission ElectronMicroscope (TEM) TheTransmis-sion Electron Micrographs of the thin layer of the nanocom-posites were recorded by Hitachi H-7100 TEM which oper-ated at an accelerating voltage of 100 kVThe thin layer of sam-ples was prepared by using a Reichert Jung Ultracut E mic-rotome equipped with cryosectioning unit whereas the sam-ples were sliced into thin layer of about 90 nm by a diamondknife cooled at minus120∘C with liquefied nitrogen

26 Tensile Properties Tensile properties were measuredwith Instronmachinemodel 4301 with grip attachment dista-nce of 45mm Load of 10 kN was applied at constant cros-shead speed of 5mmminminus1 Data was processed with com-puterized Instron (Software series 9 national instrumentsGPIB PC22a and NI-4882) Test specimen were preparedand stamped in accordance to ASTMD638 dumbbell param-eters Sample thickness was measure with Mitutoyo Digi-matic Indicator type IDF-112 having measuring accuracy ofplusmn0001mm

27 Flexural Properties The flexural strength and flexuralmodulus were measured with Instron Universal TestingMachine 4301 according to ASTMD790The size of the sam-ples testing is 127mm times 127mm times 3mm The crossheadspeed is 13mmmin and the support span length is 48mmData was processed with computerized Instron (Softwareseries 9 national instruments GPIB PC22a and NI-4882)

28 Izod Impact Resistance The Izod impact test was carriedout according to ASTMD256 standard using an impact tester(IZOD Impact Tester) The sample size is 635 times 127 times 3mmwhile the notch length is 254mm The energy required tobreak the samples was divided by unit area of residual cross-section of sample to obtain impact resistance value Theimpact strength (Jm) was calculated by dividing the energyobtained (J) with the thickness of specimen (m)


lativ

e int

ensit

y

3000 10002000

361128 cmminus1

340254 cmminus1

337560 cmminus1

163583 cmminus1

163308 cmminus1

79549 cmminus1


MMT K10

Nanomer PGV








4 6 8 10

10000

2500

0

Cou

nts




0

20

40

60

80

100

120

0 200 400 600 800 1000 1200

Wei

ght (

)

MMT K10PGV

Temperature (∘C)







MMT K10PGV

0 200 400 600 800 1000 1200

minus350E minus 04

minus300E minus 04

minus250E minus 04

minus200E minus 04

minus150E minus 04

minus100E minus 04

minus500E minus 05

000E + 00


Rela

tive i

nten

sity

PLAPCL

PLAPCLMMT K10

PLAPCLPGV

3000 10002000

174829 cmminus1

174835 cmminus1

174791 cmminus1

327983 cmminus1






Rela

tive i

nten

sity

5 102120579 (∘)

MMT K10-PLA-PCL (7)

MMT K10-PLA-PCL (5)

MMT K10-PLA-PCL (3)

MMT K10-PLA-PCL (1)

MMT K10


Rela

tive i

nten

sity

5 102120579 (∘)

NPGV-PLA-PCL (7)

NPGV-PLA-PCL (5)

NPGV-PLA-PCL (3)

NPGV-PLA-PCL (1)

NPGV






100 nm

(a)

100 nm

(b)






0

10

20

30

40

50

60

0 2 4 6 8

Tens

ile st

reng

th (M

Pa)

Clay loading ()

MMT K10PGV





MMT K10PGV

0

200

400

600

800

1000

1200

0 2 4 6 8

Tens

ile m

odul

us (M

Pa)

Clay loading ()






0

1

2

3

4

5

6

0 2 4 6 8

Elon

gatio

n at

bre

ak (m

m)

Clay loading ()

MMT K10PGV


0

10

20

30

40

50

60

0 2 4 6 8

Flex

ural

stre

ngth

(MPa

)

Clay loading ()

MMT K10PGV





0

500

1000

1500

2000

2500

3000

3500

0 2 4 6 8

Flex

ural

mod

ulus

(MPa

)

Clay loading ()

MMT K10PGV



MMT K10PGV

0

50

100

150

200

250

300

350

400

450

Impa

ct st

reng

th (J

m)




0

20

40

60

80

100

120

0 200 400 600 800

Wei

ght (

)

PLAPCLMMT K10PGV

Temperature (∘C)






PLAPCLMMT K10PGV

0 200 400 600 800

minus350E minus 03

minus300E minus 03

minus250E minus 03

minus200E minus 03

minus150E minus 03

minus100E minus 03

minus500E minus 04

000E + 00

500E minus 04


0

10000

20000

30000

40000

50000

60000

70000

80000

90000


PLAPCLMMT K10PGV

Temperature (∘C)

Stor

age m

odul

usG

998400(P

a)




0

2000

4000

6000

8000

10000

12000


PLAPCLMMT K10PGV

Temperature (∘C)

Stor

age m

odul

usG

998400998400(P

a)


0

05

1

15

2

25

3

35

tan120575


PLAPCLMMT K10PGV

Temperature (∘C)





(a) (b) (c)






4 Conclusion





Acknowledgments


References













































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




lativ

e int

ensit

y

3000 10002000

361128 cmminus1

340254 cmminus1

337560 cmminus1

163583 cmminus1

163308 cmminus1

79549 cmminus1


MMT K10

Nanomer PGV








4 6 8 10

10000

2500

0

Cou

nts




0

20

40

60

80

100

120

0 200 400 600 800 1000 1200

Wei

ght (

)

MMT K10PGV

Temperature (∘C)







MMT K10PGV

0 200 400 600 800 1000 1200

minus350E minus 04

minus300E minus 04

minus250E minus 04

minus200E minus 04

minus150E minus 04

minus100E minus 04

minus500E minus 05

000E + 00


Rela

tive i

nten

sity

PLAPCL

PLAPCLMMT K10

PLAPCLPGV

3000 10002000

174829 cmminus1

174835 cmminus1

174791 cmminus1

327983 cmminus1






Rela

tive i

nten

sity

5 102120579 (∘)

MMT K10-PLA-PCL (7)

MMT K10-PLA-PCL (5)

MMT K10-PLA-PCL (3)

MMT K10-PLA-PCL (1)

MMT K10


Rela

tive i

nten

sity

5 102120579 (∘)

NPGV-PLA-PCL (7)

NPGV-PLA-PCL (5)

NPGV-PLA-PCL (3)

NPGV-PLA-PCL (1)

NPGV






100 nm

(a)

100 nm

(b)






0

10

20

30

40

50

60

0 2 4 6 8

Tens

ile st

reng

th (M

Pa)

Clay loading ()

MMT K10PGV





MMT K10PGV

0

200

400

600

800

1000

1200

0 2 4 6 8

Tens

ile m

odul

us (M

Pa)

Clay loading ()






0

1

2

3

4

5

6

0 2 4 6 8

Elon

gatio

n at

bre

ak (m

m)

Clay loading ()

MMT K10PGV


0

10

20

30

40

50

60

0 2 4 6 8

Flex

ural

stre

ngth

(MPa

)

Clay loading ()

MMT K10PGV





0

500

1000

1500

2000

2500

3000

3500

0 2 4 6 8

Flex

ural

mod

ulus

(MPa

)

Clay loading ()

MMT K10PGV



MMT K10PGV

0

50

100

150

200

250

300

350

400

450

Impa

ct st

reng

th (J

m)




0

20

40

60

80

100

120

0 200 400 600 800

Wei

ght (

)

PLAPCLMMT K10PGV

Temperature (∘C)






PLAPCLMMT K10PGV

0 200 400 600 800

minus350E minus 03

minus300E minus 03

minus250E minus 03

minus200E minus 03

minus150E minus 03

minus100E minus 03

minus500E minus 04

000E + 00

500E minus 04


0

10000

20000

30000

40000

50000

60000

70000

80000

90000


PLAPCLMMT K10PGV

Temperature (∘C)

Stor

age m

odul

usG

998400(P

a)




0

2000

4000

6000

8000

10000

12000


PLAPCLMMT K10PGV

Temperature (∘C)

Stor

age m

odul

usG

998400998400(P

a)


0

05

1

15

2

25

3

35

tan120575


PLAPCLMMT K10PGV

Temperature (∘C)





(a) (b) (c)






4 Conclusion





Acknowledgments


References













































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




MMT K10PGV

0 200 400 600 800 1000 1200

minus350E minus 04

minus300E minus 04

minus250E minus 04

minus200E minus 04

minus150E minus 04

minus100E minus 04

minus500E minus 05

000E + 00


Rela

tive i

nten

sity

PLAPCL

PLAPCLMMT K10

PLAPCLPGV

3000 10002000

174829 cmminus1

174835 cmminus1

174791 cmminus1

327983 cmminus1






Rela

tive i

nten

sity

5 102120579 (∘)

MMT K10-PLA-PCL (7)

MMT K10-PLA-PCL (5)

MMT K10-PLA-PCL (3)

MMT K10-PLA-PCL (1)

MMT K10


Rela

tive i

nten

sity

5 102120579 (∘)

NPGV-PLA-PCL (7)

NPGV-PLA-PCL (5)

NPGV-PLA-PCL (3)

NPGV-PLA-PCL (1)

NPGV






100 nm

(a)

100 nm

(b)






0

10

20

30

40

50

60

0 2 4 6 8

Tens

ile st

reng

th (M

Pa)

Clay loading ()

MMT K10PGV





MMT K10PGV

0

200

400

600

800

1000

1200

0 2 4 6 8

Tens

ile m

odul

us (M

Pa)

Clay loading ()






0

1

2

3

4

5

6

0 2 4 6 8

Elon

gatio

n at

bre

ak (m

m)

Clay loading ()

MMT K10PGV


0

10

20

30

40

50

60

0 2 4 6 8

Flex

ural

stre

ngth

(MPa

)

Clay loading ()

MMT K10PGV





0

500

1000

1500

2000

2500

3000

3500

0 2 4 6 8

Flex

ural

mod

ulus

(MPa

)

Clay loading ()

MMT K10PGV



MMT K10PGV

0

50

100

150

200

250

300

350

400

450

Impa

ct st

reng

th (J

m)




0

20

40

60

80

100

120

0 200 400 600 800

Wei

ght (

)

PLAPCLMMT K10PGV

Temperature (∘C)






PLAPCLMMT K10PGV

0 200 400 600 800

minus350E minus 03

minus300E minus 03

minus250E minus 03

minus200E minus 03

minus150E minus 03

minus100E minus 03

minus500E minus 04

000E + 00

500E minus 04


0

10000

20000

30000

40000

50000

60000

70000

80000

90000


PLAPCLMMT K10PGV

Temperature (∘C)

Stor

age m

odul

usG

998400(P

a)




0

2000

4000

6000

8000

10000

12000


PLAPCLMMT K10PGV

Temperature (∘C)

Stor

age m

odul

usG

998400998400(P

a)


0

05

1

15

2

25

3

35

tan120575


PLAPCLMMT K10PGV

Temperature (∘C)





(a) (b) (c)






4 Conclusion





Acknowledgments


References













































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




100 nm

(a)

100 nm

(b)






0

10

20

30

40

50

60

0 2 4 6 8

Tens

ile st

reng

th (M

Pa)

Clay loading ()

MMT K10PGV





MMT K10PGV

0

200

400

600

800

1000

1200

0 2 4 6 8

Tens

ile m

odul

us (M

Pa)

Clay loading ()






0

1

2

3

4

5

6

0 2 4 6 8

Elon

gatio

n at

bre

ak (m

m)

Clay loading ()

MMT K10PGV


0

10

20

30

40

50

60

0 2 4 6 8

Flex

ural

stre

ngth

(MPa

)

Clay loading ()

MMT K10PGV





0

500

1000

1500

2000

2500

3000

3500

0 2 4 6 8

Flex

ural

mod

ulus

(MPa

)

Clay loading ()

MMT K10PGV



MMT K10PGV

0

50

100

150

200

250

300

350

400

450

Impa

ct st

reng

th (J

m)




0

20

40

60

80

100

120

0 200 400 600 800

Wei

ght (

)

PLAPCLMMT K10PGV

Temperature (∘C)






PLAPCLMMT K10PGV

0 200 400 600 800

minus350E minus 03

minus300E minus 03

minus250E minus 03

minus200E minus 03

minus150E minus 03

minus100E minus 03

minus500E minus 04

000E + 00

500E minus 04


0

10000

20000

30000

40000

50000

60000

70000

80000

90000


PLAPCLMMT K10PGV

Temperature (∘C)

Stor

age m

odul

usG

998400(P

a)




0

2000

4000

6000

8000

10000

12000


PLAPCLMMT K10PGV

Temperature (∘C)

Stor

age m

odul

usG

998400998400(P

a)


0

05

1

15

2

25

3

35

tan120575


PLAPCLMMT K10PGV

Temperature (∘C)





(a) (b) (c)






4 Conclusion





Acknowledgments


References













































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




MMT K10PGV

0

200

400

600

800

1000

1200

0 2 4 6 8

Tens

ile m

odul

us (M

Pa)

Clay loading ()






0

1

2

3

4

5

6

0 2 4 6 8

Elon

gatio

n at

bre

ak (m

m)

Clay loading ()

MMT K10PGV


0

10

20

30

40

50

60

0 2 4 6 8

Flex

ural

stre

ngth

(MPa

)

Clay loading ()

MMT K10PGV





0

500

1000

1500

2000

2500

3000

3500

0 2 4 6 8

Flex

ural

mod

ulus

(MPa

)

Clay loading ()

MMT K10PGV



MMT K10PGV

0

50

100

150

200

250

300

350

400

450

Impa

ct st

reng

th (J

m)




0

20

40

60

80

100

120

0 200 400 600 800

Wei

ght (

)

PLAPCLMMT K10PGV

Temperature (∘C)






PLAPCLMMT K10PGV

0 200 400 600 800

minus350E minus 03

minus300E minus 03

minus250E minus 03

minus200E minus 03

minus150E minus 03

minus100E minus 03

minus500E minus 04

000E + 00

500E minus 04


0

10000

20000

30000

40000

50000

60000

70000

80000

90000


PLAPCLMMT K10PGV

Temperature (∘C)

Stor

age m

odul

usG

998400(P

a)




0

2000

4000

6000

8000

10000

12000


PLAPCLMMT K10PGV

Temperature (∘C)

Stor

age m

odul

usG

998400998400(P

a)


0

05

1

15

2

25

3

35

tan120575


PLAPCLMMT K10PGV

Temperature (∘C)





(a) (b) (c)






4 Conclusion





Acknowledgments


References













































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




0

500

1000

1500

2000

2500

3000

3500

0 2 4 6 8

Flex

ural

mod

ulus

(MPa

)

Clay loading ()

MMT K10PGV



MMT K10PGV

0

50

100

150

200

250

300

350

400

450

Impa

ct st

reng

th (J

m)




0

20

40

60

80

100

120

0 200 400 600 800

Wei

ght (

)

PLAPCLMMT K10PGV

Temperature (∘C)






PLAPCLMMT K10PGV

0 200 400 600 800

minus350E minus 03

minus300E minus 03

minus250E minus 03

minus200E minus 03

minus150E minus 03

minus100E minus 03

minus500E minus 04

000E + 00

500E minus 04


0

10000

20000

30000

40000

50000

60000

70000

80000

90000


PLAPCLMMT K10PGV

Temperature (∘C)

Stor

age m

odul

usG

998400(P

a)




0

2000

4000

6000

8000

10000

12000


PLAPCLMMT K10PGV

Temperature (∘C)

Stor

age m

odul

usG

998400998400(P

a)


0

05

1

15

2

25

3

35

tan120575


PLAPCLMMT K10PGV

Temperature (∘C)





(a) (b) (c)






4 Conclusion





Acknowledgments


References













































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




PLAPCLMMT K10PGV

0 200 400 600 800

minus350E minus 03

minus300E minus 03

minus250E minus 03

minus200E minus 03

minus150E minus 03

minus100E minus 03

minus500E minus 04

000E + 00

500E minus 04


0

10000

20000

30000

40000

50000

60000

70000

80000

90000


PLAPCLMMT K10PGV

Temperature (∘C)

Stor

age m

odul

usG

998400(P

a)




0

2000

4000

6000

8000

10000

12000


PLAPCLMMT K10PGV

Temperature (∘C)

Stor

age m

odul

usG

998400998400(P

a)


0

05

1

15

2

25

3

35

tan120575


PLAPCLMMT K10PGV

Temperature (∘C)





(a) (b) (c)






4 Conclusion





Acknowledgments


References













































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




(a) (b) (c)






4 Conclusion





Acknowledgments


References













































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials














































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials













CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials










CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials



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